Process for the solvent-induced crystallization of amorphous poly(etheretherketone)-type polymers and the article formed thereby

Abstract

The present invention relates to a process for the solvent-induced crystallization of amorphous poly(etheretherketone)-type polymer to produce an article, which process comprises: A. contacting a preformed article of a polymer comprising amorphous poly(etheretherketone)-type polymer with at least one organic compound in its liquid state which consists essentially of atoms of carbon and hydrogen, optionally with oxygen, nitrogen, sulfur, halogen or mixtures thereof having a molecular weight of between about 160 and 320 daltons at a temperature of between about 85° C. and 145° C. for a time effective to crystallize the poly(etheretherketone)-type polymer, B. removing the organic compound, and C. recovering the article comprising crystallized poly(etheretherketone)-type polymer. Poly(etheretherketone), poly(phenylenesulfide) or mixtures thereof are preferred polymer systems. This process requires a much lower temperature than those necessary to prepare crystallized polymers by thermal annealing procedures. The polymers are useful in dialysis and ultrafiltration. The polymer article having a trace of the organic compound is also described.

We claim: 
     
       1. A process for the solvent-induced crystallization of amorphous poly(etheretherketone)-type polymers to produce an article comprising the solvent-induced crystalline poly(etheretherketone)-type polymer, which process comprises: A. contacting a preformed article of a polymer comprising amorphous poly(etheretherketone-type polymer with an effective amount of at least one organic compound in its liquid state which organic compound consists essentially of atoms of carbon, hydrogen, oxygen, nitrogen sulfur, halogen or mixtures thereof having a molecular weight of between about 160 and 320 daltons at a temperature below the polymer glass transition temperature Tg wherein the temperature of contact is between about 85° C. and 145° C. for a time effective to first swell and plasticize the amorphous polymer in physical contact with the organic compound and subsequently crystallize the amorphous poly(etheretherketone)-type polymer, without destroying the physical form characteristic of the preformed article prior to contact with said organic compound,   B. removing the organic compound under conditions effective to maintain the solvent-induced crystalline polymer in the preformed article form, and   C. recovering the preformed article comprising solventinduced crystalline poly(etheretherketone)-type polymer.   
     
     
       2. The process of claim 1 wherein the poly(etheretherketone)-type polymer is selected from poly(etheretherketone) (PEEK), poly(etherketone) (PEK), poly(aryletherketone) (PAEK), poly(phenylene sulfide) (PPS), poly(etherketoneketone) (PEKK), poly(etheretheretherketone) (PEEEK), poly(etheretherketoneetherketone) (PEEKEK), poly(etheretherketoneketone) (PEEKK), poly(etherketoneetherketoneketone) (PEKEKK), or mixtures or copolymers thereof. 
     
     
       3. The process of claim 1 wherein the polymer comprises poly(etheretherketone) or a phenylene substituted poly (etheretherketone). 
     
     
       4. The process of claim 1 wherein the polymer comprises poly(phenylenesulfide) or a phenylene substituted poly (phenylenesulfide). 
     
     
       5. The process of claim 1 wherein in Step (A) the contact time is between about 0.10 and 150 hours. 
     
     
       6. The process of claim 1 wherein in Step (A) the temperature is about 115° C., and the time is between 24 and 100 hours. 
     
     
       7. The process of claim 1 wherein in Step (A) the at least one organic compound is selected from fluoranthene, m-terphenyl, o-terphenyl, benzophenone, 1-cyclohexyl-2-pyrrolidinone, 1-benzyl-2-pyrrolidinone, 1-phenyl-2-pyrrolidinone, 1-chloronaphthalene, 2-benzoylnaphthalene, diphenyl sulfone, 2,5-diphenyl-1,3,4-oxadiazole, 2,6-diphenylphenol, 4,4'-dimethoxybenzophenone, 2,5-diphenyloxazole, diphenyl phthalate, 2-biphenylcarboxylic acid, 4-benzoylbiphenyl, triphenylmethane, 1,2-dibenzoylbenzene, dibenzoylmethane, pentafluorophenol, o,o'-biphenol, dibenzothiophene, phenanthrene, 4-bromodiphenyl ether, 4-bromobiphenyl, 1-benzoyl-4-piperidone, N,N-diphenylformamide, 3-phenoxybenzyl alcohol, 9-fluorenone, benzil, 1-phenylnaphthalene, pyrene, 4,4'-isopropylidenediphenol, or mixtures thereof. 
     
     
       8. The process of claim 1 wherein the at least one organic compound is selected from fluoranthene, m-terphenyl, 1-cyclohexyl-2-pyrrolidinone, benzophenone or mixtures thereof. 
     
     
       9. The process of claim 1 wherein the time is between about 12 and 100 hrs and the temperature is between about 105° and 130° C. 
     
     
       10. The process of claim 9 wherein the poly(etheretherketone)-type polymer is selected from poly(etheretherketone), poly(phenylenesulfide) or mixtures thereof, and the at least one organic compound is selected from fluoranthene, m-terphenyl, 1-cyclohexyl-2-pyrrolidinone, benzophenone or mixtures thereof. 
     
     
       11. The article produced by the process of claim 1. 
     
     
       12. The article produced by the process of claim 11 wherein said article is selected from a film, membrane, sheet, solid or hollow fiber. 
     
     
       13. The article of claim 12 wherein said article is porous permeable, semi-permeable or selectively permeable. 
     
     
       14. The article of claim 11 wherein the crystalline polymer is present homogenously throughout said article. 
     
     
       15. The article of claim 11 wherein the crystalline polymer is present as a thin layer on the surfaces of said article. 
     
     
       16. An article produced by the process of claim 1 comprising a polymer composition consisting essentially of crystallized poly(etheretherketone)-type polymer and a trace amount of the at least one residual organic compound used in solvent-induced crystallization which organic compound itself consists essentially of atoms of carbon, hydrogen, oxygen, nitrogen, sulfur, halogen or mixtures thereof having a molecular weight of between about 160 and 320 daltons and the organic compound is a liquid between about 85° and 145° C. 
     
     
       17. The polymer composition of claim 16 wherein the at least one residual organic compound is selected from fluoranthene, m-terphenyl, o-terphenyl, benzophenone, 1-cyclohexyl-2-pyrrolidinone, 1-benzyl-2-pyrrolidinone, 1-phenyl-2-pyrrolidinone, 1-chloronaphthalene, 2-benzoylnaphthalene, diphenyl sulfone, 2,5-diphenyl-1,3,4-oxadiazole, 2,6-diphenylphenol, 4,4'-dimethoxybenzophenone, 2,5-diphenyloxazole, diphenyl phthalate, 2-biphenylcarboxylic acid, 4-benzoylbiphenyl, triphenylmethane, 1,2-dibenzoylbenzene, dibenzoylmethane, pentafluorophenol, o,o'-biphenol, dibenzothiophene, phenanthrene, 4-bromodiphenyl ether, 4-bromobiphenyl, 1-benzoyl-4-piperidone, N,N-diphenylformamide, 3-phenoxybenzyl alcohol, 9-fluorenone, benzil, 1-phenylnaphthalene, pyrene, 4,4'-isopropylidenediphenol, or mixtures thereof. 
     
     
       18. The polymer composition of claim 17 wherein the poly(etheretherketone)-type polymer is selected from poly(etheretherketone), poly(phenylenesulfide) or mixtures thereof. 
     
     
       19. The polymer composition of claim 18 wherein the poly(etheretherketone)-type polymer is poly(etheretherketone). 
     
     
       20. The polymer composition of claim 18 wherein the poly(etheretherketone)-type polymer is poly(phenylenesulfide).